Exploring asymmetry induced entropy in tetraalkylammonium-urea DES systems: what can be learned from inelastic neutron scattering?

In this work, inelastic neutron scattering (INS) spectroscopy is used to investigate the impact of entropic factors on the behaviour of deep eutectic solvents (DES). Periodic density functional theory calculations (DFT) provide a reliable assignment of the vibrational modes of pure compounds. This assignment guides the analysis of INS spectra of binary mixtures - with particular attention to methyl torsional modes. Deviations from ideality in the mixtures of tetraalkylammonium salts with urea are readily determined through a simplified thermodynamic approach. This study reports and discusses the relationship between the cation's asymmetry, the INS spectra of the eutectic mixture and its deviation from ideality. Contrary to the majority of systems studied so far, the deep eutectic system comprised of [N2,2,2,1]Cl and urea appears to owe its deviation from ideality to entropic rather than enthalpic factors.

Intermolecular Interactions in 3-Aminopropyltrimethoxysilane, N-Methyl-3-aminopropyltrimethoxysilane and 3-Aminopropyltriethoxysilane: Insights from Computational Spectroscopy.

In this work, a computational spectroscopy approach was used to provide a complete assignment of the inelastic neutron scattering spectra of three title alkoxysilane derivatives-3-aminopropyltrimethoxysilane (APTS), N-methyl-3-aminopropyltrimethoxysilane (MAPTS), and 3-aminopropyltriethoxysilane (APTES). The simulated spectra obtained from density functional theory (DFT) calculations exhibit a remarkable match with the experimental spectra. The description of the experimental band profiles improves as the number of molecules considered in the theoretical model increases, from monomers to trimers. This highlights the significance of incorporating non-covalent interactions, encompassing classical NH···N, N-H···O, as well as C-H···N and C-H···O hydrogen bond contacts, to achieve a comprehensive understanding of the system. A distinct scenario emerges when considering optical vibrational techniques, infrared and Raman spectroscopy. In these instances, the monomer model provides a reasonable description of the experimental spectra, and no substantial alterations are observed in the simulated spectra when employing dimer and trimer models. This observation underscores the distinctive ability of neutron spectroscopy in combination with DFT calculations in assessing the structure and dynamics of molecular materials.

Corrigendum: Comparison of 3DCRT and IMRT out-of-field doses in pediatric patients using Monte Carlo simulations with treatment planning system calculations and measurements.

[This corrects the article DOI: 10.3389/fonc.2022.879167.].

Bidimensional ensemble entropy: Concepts and application to emphysema lung computerized tomography scans.

BACKGROUND AND OBJECTIVE: Bidimensional entropy algorithms provide meaningful quantitative information on image textures. These algorithms have the advantage of relying on well-known one-dimensional entropy measures dedicated to the analysis of time series. However, uni- and bidimensional algorithms require the adjustment of some parameters that influence the obtained results or even findings. To address this, ensemble entropy techniques have recently emerged as a solution for signal analysis, offering greater stability and reduced bias in data patterns during entropy estimation. However, such algorithms have not yet been extended to their two-dimensional forms. METHODS: We therefore propose six bidimensional algorithms, namely ensemble sample entropy, ensemble permutation entropy, ensemble dispersion entropy, ensemble distribution entropy, and two versions of ensemble fuzzy entropy based on different models or parameters initialization of an entropy algorithm. These new measures are first tested on synthetic images and further applied to a biomedical dataset. RESULTS: The results suggest that ensemble techniques are able to detect different levels of image dynamics and their degrees of randomness. These methods lead to more stable entropy values (lower coefficients of variations) for the synthetic data. The results also show that these new measures can obtain up to 92.7% accuracy and 88.4% sensitivity when classifying patients with pulmonary emphysema through a k-nearest neighbors algorithm. CONCLUSIONS: This is a further step towards the potential clinical deployment of bidimensional ensemble approaches to detect different levels of image dynamics and their successful performance on emphysema lung computerized tomography scans. These bidimensional ensemble entropy algorithms have potential to be used in various imaging applications thanks to their ability to distinguish more stable and less biased image patterns compared to their original counterparts.

Retinal OCT speckle as a biomarker for glaucoma diagnosis and staging.

This paper presents a novel image analysis strategy that increases the potential of macular Optical Coherence Tomography (OCT) by using speckle features as biomarkers in different stages of glaucoma. A large pool of features (480) were computed for a subset of macular OCT volumes of the Leuven eye study cohort. The dataset contained 258 subjects that were divided into four groups based on their glaucoma severity: Healthy (56), Mild (94), Moderate (48), and Severe (60). The OCT speckle features were categorized as statistical properties, statistical distributions, contrast, spatial gray-level dependence matrices, and frequency domain features. The averaged thicknesses of ten retinal layers were also collected. Kruskal-Wallis H test and multivariable regression models were used to infer the most significant features related to glaucoma severity classification and to the correlation with visual field mean deviation. Four features were selected as being the most relevant: the ganglion cell layer (GCL) and the inner plexiform layer (IPL) thicknesses, and two OCT speckle features, the data skewness computed on the retinal nerve fiber layer (RNFL) and the scale parameter (a) of the generalized gamma distribution fitted to the GCL data. Based on a significance level of 0.05, the regression models revealed that RNFL skewness exhibited the highest significance among the features considered for glaucoma severity staging (p-values of 8.6×10-6 for the logistic model and 2.8×10-7 for the linear model). Furthermore, it demonstrated a strong negative correlation with the visual field mean deviation (ρ=-0.64). The post hoc analysis revealed that, when distinguishing healthy controls from glaucoma subjects, GCL thickness is the most relevant feature (p-value of 8.7×10-5). Conversely, when comparing the Mild versus Moderate stages of glaucoma, RNFL skewness emerged as the only feature exhibiting statistical significance (p-value = 0.001). This work shows that macular OCT speckle contains information that is currently not used in clinical practice, and not only complements structural measurements (thickness) but also has a potential for glaucoma staging.

Targeted radionuclide therapy directed to the tumor phenotypes: A dosimetric approach using MC simulations.

BACKGROUND: In Targeted Radionuclide Therapy (TRT), the continuous technological effort in imaging tumor phenotypes (i.e. sub-volumes with different phenotypic characteristics) and in precise radiopharmaceutical tumor-targeting, is allowing for a better dosimetric optimization at the tumor phenotype level. The aim of this study was to evaluate the dosimetric efficiency (considering strategic absorbed dose delivery to the phenotypes) of personalized TRT directed to the tumor phenotypes. METHODS: The dosimetric assessment was performed using a four-phenotype realistic tumor model implemented within the ICRP reference voxel phantom and simulations using the state-of-the-art Monte Carlo program PENELOPE. The dose assessment was performed for five radionuclides commonly used in therapy and/or diagnostic procedures: 125I, 99mTc, 177Lu, 161Tb and 67Ga. Two irradiation scenarios were considered: (i) the Whole Tumor Treatment Planning Scenario (WTTPS), i.e. the four phenotypes irradiated with the same radionuclide; (ii) the Phenotype Treatment Planning Scenario (PTPS), i.e. each phenotype irradiated by a single radionuclide. The optimal radionuclide configurations were studied considering the maximization of the absorbed dose delivered to the tumor and the minimization of dose to healthy tissues. RESULTS: In WTTPS, 125I outperforms the other radionuclides in terms of the ratio of the maximum absorbed dose delivered to the tumor and the minimum absorbed dose delivered to healthy tissues. In the PTPS, the use of 161Tb in combination with the other radionuclides maximizes the absorbed dose in the tumor tissues while simultaneously minimizing dose to healthy tissue, compared to the WTTPS. In agreement with recent pre-clinical studies, our computational results confirm and indicate the beneficial additive dosimetric effects of Auger and conversion electrons of 161Tb with respect to 177Lu, when considering the same cumulated activity for both. Interestingly, in considering a realistic tumor model, the better dosimetric performances of 161Tb were confirmed also for tumor volumes ranging from 1.98 cm3 to 33.32 cm3. CONCLUSIONS: Dose assessment in realistic non-homogeneous tumor models could provide more insights with respect to consider only homogenous water-spheres tumor models and should be taken into account in dosimetry-based TRT planning studies.

From PEF to PBF: What difference does the longer alkyl chain make a computational spectroscopy study of poly(butylene 2,5-furandicarboxylate).

This work explores the conformational preferences and the structure-property correlations of poly(butylene 2,5-furandicarboxylate) (PBF), a longer chain analogue of the most well-known biobased polyester from the furan family, poly(ethylene 2,5-furandicarboxylate) (PEF). A thorough computational spectroscopic study-including infrared, Raman and inelastic neutron scattering spectroscopy, combined with discrete and periodic density functional theory calculations-allowed the identification of dominant structural motifs in the amorphous and crystalline regions. Discrete calculations and vibrational spectroscopy of semi-crystalline and amorphous samples strongly support the predominance of gauche, trans, gauche conformations of the butylene glycol fragment in both the crystalline and amorphous domains. In what concerns the furandicarboxylate fragment, amorphous domains are dominated by syn,syn conformations, while in the crystalline domains the anti,anti forms prevail. A possible crystalline structure-built from these conformational preferences and including a network of C-H···O hydrogen bond contacts-was optimized using periodic density functional theory. This proposed crystal structure avoids the unrealistic structural features of the previously proposed X-ray structure, provides an excellent description of the inelastic neutron scattering spectrum of the semi-crystalline form, and allows the correlation between microscopic structure and macroscopic properties of the polymer.

Structural Dynamics of Chloromethanes through Computational Spectroscopy: Combining INS and DFT.

In this work, the structural dynamics of the chloromethanes CCl4, CHCl3 and CH2Cl2 were evaluated through a computational spectroscopy approach by comparing experimental inelastic neutron scattering (INS) spectra with the corresponding simulated spectra obtained from periodic DFT calculations. The overall excellent agreement between experimental and calculated spectra allows a confident assignment of the vibrational features, including not only the molecular fundamental modes but also lattice and combination modes. In particular, an impressive overtone sequence for CHCl3 is fully described by the simulated INS spectrum. In the CCl4 spectrum, the splitting of the ν3 mode at ca. 765-790 cm-1 is discussed on the basis of the Fermi resonance vs. crystal splitting controversy.

Comparison of 3DCRT and IMRT out-of-field doses in pediatric patients using Monte Carlo simulations with treatment planning system calculations and measurements.

3DCRT and IMRT out-of-field doses in pediatric patients were compared using Monte Carlo simulations with treatment planning system calculations and measurements. Purpose: Out-of-field doses are given to healthy tissues, which may allow the development of second tumors. The use of IMRT in pediatric patients has been discussed, as it leads to a "bath" of low doses to large volumes of out-of-field organs and tissues. This study aims to compare out-of-field doses in pediatric patients comparing IMRT and 3DCRT techniques using measurements, Monte Carlo (MC) simulations, and treatment planning system (TPS) calculations. Materials and methods: A total dose of 54 Gy was prescribed to a PTV in the brain of a pediatric anthropomorphic phantom, for both techniques. To assess the out-of-field organ doses for both techniques, two treatment plans were performed with the 3DCRT and IMRT techniques in TPS. Measurements were carried out in a LINAC using a pediatric anthropomorphic phantom and thermoluminescent dosimeters to recreate the treatment plans, previously performed in the TPS. A computational model of a LINAC, the associated multileaf collimators, and a voxelized pediatric phantom implemented in the Monte Carlo N-Particle 6.1 computer program were also used to perform MC simulations of the out-of-field organ doses, for both techniques. Results: The results obtained by measurements and MC simulations indicate a significant increase in dose using the IMRT technique when compared to the 3DCRT technique. More specifically, measurements show higher doses with IMRT, namely, in right eye (13,041 vs. 593 mGy), left eye (6,525 vs. 475 mGy), thyroid (79 vs. 70 mGy), right lung (37 vs. 28 mGy), left lung (27 vs. 20 mGy), and heart (31 vs. 25 mGy). The obtained results indicate that out-of-field doses can be seriously underestimated by TPS. Discussion: This study presents, for the first time, out-of-field dose measurements in a realistic scenario and calculations for IMRT, centered on a voxelized pediatric phantom and an MC model of a medical LINAC, including MLC with log file-based simulations. The results pinpoint significant discrepancies in out-of-field doses for the two techniques and are a cause of concern because TPS calculations cannot accurately predict such doses. The obtained doses may presumably increase the risk of development of second tumors.

Colored Texture Analysis Fuzzy Entropy Methods with a Dermoscopic Application.

Texture analysis is a subject of intensive focus in research due to its significant role in the field of image processing. However, few studies focus on colored texture analysis and even fewer use information theory concepts. Entropy measures have been proven competent for gray scale images. However, to the best of our knowledge, there are no well-established entropy methods that deal with colored images yet. Therefore, we propose the recent colored bidimensional fuzzy entropy measure, FuzEnC2D, and introduce its new multi-channel approaches, FuzEnV2D and FuzEnM2D, for the analysis of colored images. We investigate their sensitivity to parameters and ability to identify images with different irregularity degrees, and therefore different textures. Moreover, we study their behavior with colored Brodatz images in different color spaces. After verifying the results with test images, we employ the three methods for analyzing dermoscopic images of malignant melanoma and benign melanocytic nevi. FuzEnC2D, FuzEnV2D, and FuzEnM2D illustrate a good differentiation ability between the two-similar in appearance-pigmented skin lesions. The results outperform those of a well-known texture analysis measure. Our work provides the first entropy measure studying colored images using both single and multi-channel approaches.

Chemical Composition of the "Galo de Barcelos" (Barcelos Rooster Raw Meat).

Ten roosters produced according to "Barcelos Confraria" rules and ten roosters of autochthonous "Amarela" breed, reared on a similar traditional production system, were analyzed, and the chemical profile of two of the most significant meat portions, breast and drumstick, was determined. The results demonstrated that the "Barcelos" rooster raw meat is rich in proteins (22.3%) and fat (4.31%), particularly in monounsaturated fatty acids (39.1%). Significant differences (p ≤ 0.01) were observed, with the breast having a higher protein content (25.1 vs. 19.7%) and less fat (1.9% vs. 6.7%), compared to the drumstick. The fatty acid profile revealed (SFA 30.0%, MUFA 39.1%, and PUFA 24.6%) a similar composition to the roosters reared in the traditional or organic production systems, such as the "Amarela" autochthonous rooster. The "Barcelos" rooster can be regarded as a highly nutritional meat, with an interesting chemical profile ensuring a high-quality traditional product to consumers.

Automatic Segmentation of the Optic Nerve Head Region in Optical Coherence Tomography: A Methodological Review.

The optic nerve head (ONH) represents the intraocular section of the optic nerve, which is prone to damage by intraocular pressure (IOP). The advent of optical coherence tomography (OCT) has enabled the evaluation of novel ONH parameters, namely the depth and curvature of the lamina cribrosa (LC). Together with the Bruch's membrane minimum-rim-width (BMO-MRW), these seem to be promising ONH parameters for diagnosis and monitoring of retinal diseases such as glaucoma. Nonetheless, these OCT derived biomarkers are mostly extracted through manual segmentation, which is time-consuming and prone to bias, thus limiting their usability in clinical practice. The automatic segmentation of ONH in OCT scans could further improve the current clinical management of glaucoma and other diseases. This review summarizes the current state-of-the-art in automatic segmentation of the ONH in OCT. PubMed and Scopus were used to perform a systematic review. Additional works from other databases (IEEE, Google Scholar and ARVO IOVS) were also included, resulting in a total of 29 reviewed studies. For each algorithm, the methods, the size and type of dataset used for validation, and the respective results were carefully analysed. The results show a lack of consensus regarding the definition of segmented regions, extracted parameters and validation approaches, highlighting the importance and need of standardized methodologies for ONH segmentation. Only with a concrete set of guidelines, these automatic segmentation algorithms will build trust in data-driven segmentation models and be able to enter clinical practice.

Signal-carrying speckle in optical coherence tomography: a methodological review on biomedical applications.

SIGNIFICANCE: Speckle has historically been considered a source of noise in coherent light imaging. However, a number of works in optical coherence tomography (OCT) imaging have shown that speckle patterns may contain relevant information regarding subresolution and structural properties of the tissues from which it is originated. AIM: The objective of this work is to provide a comprehensive overview of the methods developed for retrieving speckle information in biomedical OCT applications. APPROACH: PubMed and Scopus databases were used to perform a systematic review on studies published until December 9, 2021. From 146 screened studies, 40 were eligible for this review. RESULTS: The studies were clustered according to the nature of their analysis, namely static or dynamic, and all features were described and analyzed. The results show that features retrieved from speckle can be used successfully in different applications, such as classification and segmentation. However, the results also show that speckle analysis is highly application-dependant, and the best approach varies between applications. CONCLUSIONS: Several of the reviewed analyses were only performed in a theoretical context or using phantoms, showing that signal-carrying speckle analysis in OCT imaging is still in its early stage, and further work is needed to validate its applicability and reproducibility in a clinical context.

Knee Dislocation With Vascular and Nerve Injury in a Professional Football Player: Return to Play.

Traumatic knee dislocations are serious and complex injuries, defined as clinical and/or radiological loss of tibiofemoral congruence, which may represent real emergencies to the integrity of the affected limb. This lesion is responsible for multi-ligament tears but the most serious possible complications are related to vascular and peripheral nerve injuries. Recent studies show that surgical treatment has better functional results and higher return rates to sports practice compared to conservative treatment. However, there is still no consensus on the ideal surgical technique and the timing of surgery. After conservative management or surgical treatment, rehabilitation treatment plays a key role in the recovery process. There are few studies evaluating the return to competition after traumatic knee dislocation and those athletes who return have difficulty reaching the pre-injury level. Here, we report the case of a professional football player who suffered a traumatic knee dislocation, with multiple ligament tears associated with vascular and neurological damage. Three hours after the initial lesion a double interposition bypass was done with the great saphenous vein, returning flow distally. It was decided not to perform ligament surgery. Two years after a long and intense rehabilitation program the athlete successfully returned to competition.

Vibrational Dynamics in crystalline 4-(dimethylamino) benzaldehyde: Inelastic Neutron Scattering and Periodic DFT Study.

The structure and dynamics of crystalline 4-(dimethylamino) benzaldehyde, 4DMAB, are assessed through INS spectroscopy combined with periodic DFT calculations. The excellent agreement between experimental and calculated spectra is the basis for a reliable assignment of INS bands. The external phonon modes of crystalline 4DMAB are quite well described by the simulated spectrum, as well as the modes involving low-frequency molecular vibrations. Crystal field splitting is predicted and observed for the modes assigned to the dimethylamino group. Concerning the torsional motion of methyl groups, four individual bands are identified and assigned to specific methyl groups in the asymmetric unit. The torsional frequencies of the four methyl groups in the asymmetric unit fall in a region of ca. 190 ± 20 cm-1, close to the range of values observed for methyl groups bonding to unsaturated carbon atoms. The hybridization state of the X atom in X-CH3 seems to play a key role in determining the methyl torsional frequency.

Neutron and Gamma-Ray Detection System Coupled to a Multirotor for Screening of Shipping Container Cargo.

In order to detect special nuclear materials and other radioactive materials in Security and Defense scenarios, normally, a combination of neutron and gamma-ray detection systems is used. In particular, to avoid illicit traffic of special nuclear materials and radioactive sources/materials, radiation portal monitors are placed at seaports to inspect shipping-container cargo. Despite their large volume (high efficiency), these detection systems are expensive, and therefore only a fraction of these containers are inspected. In this work, a novel mobile radiation detection system is presented, based on an EJ-200 plastic scintillator for the detection of gamma rays and beta particles, and a neutron detector EJ-426HD plastic scintillator (with 6Li) embedded in a compact and modular moderator. The use of silicon photomultipliers in both detectors presented advantages such as lightweight, compactness, and low power consumption. The developed detection system was integrated in a highly maneuverable multirotor. Monte Carlo simulations were validated by laboratory measurements and field tests were performed using real gamma-ray and neutron sources. The detection and localization within one meter was achieved using a maximum likelihood estimation algorithm for 137Cs sources (4 MBq), as well as the detection of 241Am-beryllium (1.45 GBq) source placed inside the shipping container.

Melanin: Production from Cheese Bacteria, Chemical Characterization, and Biological Activities.

Pigments are compounds of importance to several industries, for instance, the food industry, where they can be used as additives, color intensifiers, and antioxidants. As the current trend around the world is shifting to the use of eco-friendly commodities, demand for natural dyes is increasing. Melanins are pigments that are produced by several microorganisms. Pseudomonas putida ESACB 191, isolated from goat cheese rind, was described as a brown pigment producer. This strain produces a brown pigment via the synthetic Müeller-Hinton Broth. This brown compound was extracted, purified, analyzed by FTIR and mass spectrometry, and identified as eumelanin. The maximum productivity was 1.57 mg/L/h. The bioactivity of eumelanin was evaluated as the capacity for scavenging free radicals (antioxidant activity), EC50 74.0 ± 0.2 µg/mL, and as an acetylcholinesterase inhibitor, with IC50 575 ± 4 µg/mL. This bacterial eumelanin did not show cytotoxicity towards A375, HeLa Kyoto, HepG2, or Caco2 cell lines. The effect of melanin on cholesterol absorption and drug interaction was evaluated in order to understand the interaction of melanin present in the cheese rind when ingested by consumers. However, it had no effect either on cholesterol absorption through an intestinal simulated barrier formed by the Caco2 cell line or with the drug ezetimibe.

New Insights on the Vibrational Dynamics of 2-Methoxy-, 4-Methoxy- and 4-Ethoxy-Benzaldehyde from INS Spectra and Periodic DFT Calculations.

The dynamics of 2-methoxybenzaldehyde, 4-methoxybenzaldehyde, and 4-ethoxybenzaldehyde in the solid state are assessed through INS spectroscopy combined with periodic DFT calculations. In the absence of experimental data for 4-ethoxybenzaldehyde, a tentative crystal structure, based on its similarity with 4-methoxybenzaldehyde, is considered and evaluated. The excellent agreement between calculated and experimental spectra allows a confident assignment of the vibrational modes. Several spectral features in the INS spectra are unambiguously assigned and torsional potential barriers for the methyl groups are derived from experimental frequencies. The intramolecular nature of the potential energy barrier for methyl rotation about O-CH3 bonds compares with the one reported for torsion about saturated C-CH3 bonds. On the other hand, the intermolecular contribution to the potential energy barrier may represent 1/3 of the barrier height in these systems.

Plasmatic Oxidative and Metabonomic Profile of Patients with Different Degrees of Biliary Acute Pancreatitis Severity.

Acute pancreatitis (AP) is an inflammatory process of the pancreas with variable involvement of the pancreatic and peripancreatic tissues and remote organ systems. The main goal of this study was to evaluate the inflammatory biomarkers, oxidative stress (OS), and plasma metabolome of patients with different degrees of biliary AP severity to improve its prognosis. Twenty-nine patients with biliary AP and 11 healthy controls were enrolled in this study. We analyzed several inflammatory biomarkers, multifactorial scores, reactive oxygen species (ROS), antioxidants defenses, and the plasma metabolome of biliary AP and healthy controls. Hepcidin (1.00), CRP (0.94), and SIRI (0.87) were the most accurate serological biomarkers of AP severity. OS played a pivotal role in the initial phase of AP, with significant changes in ROS and antioxidant defenses relating to AP severity. Phenylalanine (p < 0.05), threonine (p < 0.05), and lipids (p < 0.01) showed significant changes in AP severity. The role of hepcidin and SIRI were confirmed as new prognostic biomarkers of biliary AP. OS appears to have a role in the onset and progression of the AP process. Overall, this study identified several metabolites that may predict the onset and progression of biliary AP severity, constituting the first metabonomic study in the field of biliary AP.

Evaluation of COVID-19 chest computed tomography: A texture analysis based on three-dimensional entropy.

Radiologists, and doctors in general, need relevant information for the quantification and characterization of pulmonary structures damaged by severe diseases, such as the Coronavirus disease 2019 (COVID-19). Texture-based analysis in scope of other pulmonary diseases has been used to screen, monitor, and provide valuable information for several kinds of diagnoses. To differentiate COVID-19 patients from healthy subjects and patients with other pulmonary diseases is crucial. Our goal is to quantify lung modifications in two pulmonary pathologies: COVID-19 and idiopathic pulmonary fibrosis (IPF). For this purpose, we propose the use of a three-dimensional multiscale fuzzy entropy (MFE3D) algorithm. The three groups tested (COVID-19 patients, IPF, and healthy subjects) were found to be statistically different for 9 scale factors ( p < 0.01 ). A complexity index (CI) based on the sum of entropy values is used to classify healthy subjects and COVID-19 patients showing an accuracy of 89.6 % , a sensitivity of 96.1 % , and a specificity of 76.9 % . Moreover, 4 different machine-learning models were also used to classify the same COVID-19 dataset for comparison purposes.